Patent GB-1336171-A (GB)
Title: Photographic water-insoluble compounds
IPC: G03C7/32
Filed: 1970-02-24
Abstract: 1336171 Branched-alkyl photographic compounds AGFA-GEVAERT 19 April 1971 [24 Feb 1970] 8840/70 Heading C2C [Also in Divisions C4 and G2] The invention comprises a photographic water-insoluble component containing a group that renders the component fast to diffusion in hydrophilic colloid media, the group being of formula in which X is O, S, SO 2 , CONH, NHCO, NHSO 2  or SO 2 NH, and R 1  and R 2  are C 4-12  branchedchain alkyl groups. The photographic component may be a colour coupler, a mask-former, a competing coupler or a U.V. absorber. The following components are specified and prepared:- Processes.-(1) p-Chlorothiophenol, NaOH, isohexadecyl bromide (R 1  = dimethylbutyl, R 2 = dimethylhexyl) and HBr give p-isohexadecylthio-chlorobenzene, which is oxidized by H 2 O 2  to p - isohexadecylsulphonyl - chlorobenzene, which with hydrazine yields p-isohexadeaylsulphonylphenylhydrazine, which is cyclized with #- amino-#-ethoxyacrylic acid ethyl ester to give 1 - p - isohexadecylsulphonylphenyl-3-amino- 2 - pyrazolin - 5 - one; reaction with anisidine hydrochloride gives the first product above. (2) Isohexadecyl bromide with methyl phydroxybenzoate yields, after hydrolysis, p-isohexadecyloxybenzoic acid, which with SOCl 2  gives the acid chloride, which with the appropriate 3-aminopyrazolone gives the second product above. (3), (4) Isononane carboxylic acid chloride with the appropriate 3-aminopyrazolones gives the third and fourth products above. (5) Addition of isohexadecyl mercaptan to maleic anhydride yields isohexadecylthiosuccinic anhydride, which with 5-aminoindazolone gives the fifth product above. (6) o-Nitrophenol with isohexadecyl bromide gives o-isohexadecyloxynitrobenzene, which is reduced (Raney nickel catalyst) to o-isohexadecyloxyaniline, which is condensed with p-(1,1,2-trifluoro-2- chloroethoxy)-benzoylacetic acid ethyl ester to give the sixth product above. (7) Isohexadecyl bromide and o-hydroxyacetophenone give o-isohexadecyloxy-acetophenone, which is oxidized by Br 2  to o-isohexadecyloxybenzoic acid, this is converted to the acid chloride with SOCl 2 , and sodium ethyl acetoacetate and then NaOCH 3  and methanol give methyl o-isohexadecyloxybenzoylacetate, which with 2-(p-aminophenyl)- quinazolone gives the seventh product above. (8) Iso-octadecyl alcohol [(CH 3 ) 3 CCH 2 CH(CH 3 )- CH(CH 2 OH)CH 2 CH 2 CH(CH 3 )CH 2 C(CH 3 ) 3 ] with acrylonitrile gives # - iso - octadecyloxy - propionitrile, which is hydrogenated to #-iso-octadecyloxypropylamine, which with 1-hydroxy-4-chloronaphthoic acid phenyl ester gives the eighth product above. (9) o-Isohexadecyloxybenzoylacetic acid methyl ester and p-methylsulphonylphenylhydrazine give 1 - p - methylsulphonylphenyl - 3 - o - isohexadecyloxyphenyl - 2 - pyrazolin-5-one. (10) The ninth product above is prepared from the appropriate benzoyl chloride and the appropriate aminophenyl compound (11) Isohexadecylamine is prepared from isohexadecyl bromide and liquid NH 3 , and with 1-hydroxy-4-chloronaphthoic acid phenyl ester gives the tenth product above. (12) Iso-octadecylsulphonylhydrazide is prepared from isooctadecylsulphochloride and hydrazine hydrate, and on reaction with gives the eleventh product above.